DE1669375A1 - Process for the production of colored acrylic fibers - Google Patents

Description

Dr. O. DITTMANN ^DÄ " ⁸ ? 9

K. L SHIP Dr. A. v. FUNER

PATENT LAWYERS 8 Munich 9, Beretteranger 15

Telephone 29 7369 B β 8 O h Ι ^ β ^ Ι b U, B ₁₁ R

to the patent application

of the company

ASAIIX KiVSEI KOGYO KABUSHXKX KAXSHA Osaka «Japan

concerning

Process for the production of colored Aor yjL faae rn Priorities: No. 66 566/1966, Oct 11, 1966, Japan

The invention relates to a process for the production of dyed AcTy.lfasem by cleaning, drying and subsequent steaming by spinning a solution of Aorymitrllpolymer containing a pigment, freeing the resulting threads from the solvent or desolvation. (desolvating) and stretching the same swollen gel filaments obtained by the heat at 105 to 15O ⁰ G. Furthermore, the invention relates to a process for the production of dyed acrylic fibers by cleaning, drying and then steaming by spinning a nitric acid solution sum hate spinning with a Ge «Holds an Artrylnitrilcopoiymer, consisting of at least 80 wt .-% acrylonitrile, 0.1 to 2.0 wt .-% methallylsulfonic acid and 19.9 to 0 wt .- # of an ethylenically unsaturated compound, Bowie no more than 10 wt. -% of a pigment, based on the weight of the pile / fm'B, liberation of the resulting threads from solvent bo drawing "denol" / atize and amichlleßeiulaH Γ, bracken dtiraelben In rtor Hltie arhalfceiieii gaquolloneu gel threads bsi 105 to

009049/1769 bad OBiQiNAt

150 ° 0.

The term "acrylonitrile polymer" is to be understood as meaning that they are polyacrylonitrile, copolymers, mixed polymers, graft copolymers and block copolymers consisting of no less ale 80% by weight of acrylonitrile and no more than 20% by weight of indestene Ethylenically unsaturated compound, includes · The one used here The term "ethylenically unsaturated compound" includes acrylic acid esters and methacrylic acid esters such as acrylic acid ethyleter and methyl acrylate and methacrylic acid methyl ester respectively Methyl methacrylate, vinyl esters such as vinyl acetate, amides such as acrylic acid amide, methacrylic acid amide and N-alkyl-substituted derivatives the same, styrene, vinyl chloride, vinylidene chloride, methacrylonitrile, vinyl dene cyanide, carboxylic acids such as acrylic acid, methacrylic acid and Itaconic acid, basic heterocyclic compounds such as 4-vinylpyridine and ^ -Methyl-i? -Vinylpyridine, amines such as methacrylic acid aminoethyl ester or aminoethyl methacrylate, sulfonic acids, ' such as Btyjfolnulfansäure, methacrylic acid-2-sulfoethylester or 2-sulfoäthylaethaorylat and methacrylic acid-3-aulfopropylester or 3-SulfopropQrlmethaorylat and salts the same.

The term `` acrylic fiber ¹¹ is used herein to refer to a fiber made from the acrylonitrile polymer discussed above.

It is well known that dyed Aory! Fibers are spun egg · » nui »polymer solution containing a pigment; be generated can · The colored ones produced by dao conventional methods

Acrylic fibers, however, have 2 major shortcomings. One of the same j . ^ that the Ilölbechbhiilt, especially the llaßroiö «·

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• contains, the fiber is bad and the other consists in that the hue is dull, pale or cloudy and the saturation is insufficient.

There has been an extensive and in-depth investigation to resolve the issue The above deficiency has been accomplished and the present invention is achieved. According to the invention, the Haßrelbechtheit τοη Acrylic fiber ^ increased by 1 or 2 ratings and obtained a much livelier or shinier color tone.

The method according to the invention comprises cleaning, drying and subsequent steaming of the acrylonitrile polymer containing a pigment by spinning a solution, liberation the resulting threads Tom solvent or desolvate and scatter the same swollen gel threads obtained in the heat at 105 to 150 ° C. The process according to the invention further comprises the cleaning, drying and steaming of the solution obtained by spinning a nitric acid solution containing an acrylonitrile copolymer, consisting of not less than 80% by weight of acrylonitrile, 0.1 to 2.0% by weight of methylsulfonic acid and 19.9 to ( 0 wt .-% of an ethylenically unsaturated compound, and not more than 10% by weight of a pigment, based on the weight of the named copolymer, swollen GelfSden obtained at 105 to 150 ° C.

The invention therefore relates to a method for producing dyed aoryl fibers from, by spinning, a solution of acrylonitrile polymer or an aoryl copolymer from not less than 80 wt .-% acrylonitrile, 0.1 to 2.0 wt .-% Methallylsulfonic acid and 19.9 to 0% by weight of an ethylenic acid

009849/1769 sad original ^ _{4 m}

saturated compound, containing a pigment, preferably in an amount of not more than 10% by weight, based on the polymer or copolymer, freeing the resulting threads from the solvent or desolvation and Stretching of the same swollen gel threads obtained in the heat, which is characterized in that the swollen gel threads are cleaned, dried and then at a temperature of 105 to 150 ° C steams.

You rub fastness (both the dry rub fastness and the Fire resistance) was invented according to the Japanese Industrial Standard L-1048 and the procedure mentioned Hue by stochastically treating the results of the investigation with the unarmed eyes of an amount of Workers in dyeing identified.

It was found that the rubbing fastness of dyed acrylic fibers obtained by stretching in the heat and drying by repeating the solvent removal treatment or desolvation treatment, such as washing the spun threads and a single treatment to remove them from the solvent or deaolvated threads once , chew is improved and that the rubbing fastness of the dried fibers is nevertheless improved if threads drawn in the heat are cleaned before drying. It has also been found that cleaning the threads after drying is less effective than cleaning heat-stretched and undried threads. Further, festgeci Colt that the Reibechtlieit is considerable improved, Wonn after stretching purified dried filaments further comprising a Dim, .cn are subjected as if they keiner- Γ {vaccinate untoi-vorffir CFLC-r without

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Cleaning have been subjected to steaming. For example, both the dry rub fastness and the wet rub fastness of the pigment-dyed threads of acrylonitrile polymer, which have been stretched, dried without cleaning and immediately subjected to a heat treatment, are low, in that they have a rating of 2. In addition, the dry rub fastness of the pigment-dyed threads, which are cleaned and none are subjected to heat treatment "orden, well _Φ by 5 ° is have been evaluating 4, the wet rub fastness; however, is low by having a rating of 2 to 3. Superior pigment-dyed acrylic fibers with dry and wet rub resistance with a rating of 5 can only be achieved if the threads are dried after curing and then subjected to a heat treatment, as mentioned above.

Although the mechanism of this phenomenon is not aufgekiärb is «j is concluded that it the exposure chaise longue or add something to change the number, ana AusfLüükungsgradas and degree kusgesetatseins the Pigmentteliehen which releases .lagen on the surface of the threads! And ge from fiber or Retained by the Faaers ^ structure force as judged by optical Mikrophotogi'aph.la imd Eiektroneumlki'ophotographie is related.

It has been found that the Helbechtheit a fiber changes with the kind of the acrylonitrile polymer · The authenticity of the fibers from the polymer with a content of 0.1 to 2 _e 0 wt ~% MethaiLyIsulfonsäurs lab namely higher than that of the fibers from the polymer without methailyisulferic acid, moreover, contrary to expectations, Cestge ifcatlfc, i'ciß dLe Eohthett der Pasern from the under use

from Poiyia <jpi: -i-ii; I.onalnifciatorey3teiE fc «rge ~

mm Q r »

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polymer is much better than that of fibers made from the polymer made using a different type of polymerization initiator. Such polymerization initiator systems are systems with a hydroxylamine sulfonate and a bisulfite [hydroxylamine sulfonate-a bisulfite system], etc. The effect is particularly noticeable when a copolymer bit containing methallylsulfonic acid is produced by aqueous precipitation polymerization. The above-mentioned effect was first observed in fibers prepared by wet spinning using nitric acid as a solvent, and although such tendency was later found in fibers prepared by wet spinning using a zinc chloride solution and bhodanide solution, respectively, the effect was found to be in the case of fibers prepared by wet spinning using nitric acid Solvent-made fibers as most evident.

The degree of flocculation of the pigment particles at dr. by hatred of nitric spinning solution of using d "i whether ©. <. mentioned Polyaerisationsinitiators after the above-mentioned polyether merisationoverfahrensweise prepared copolymer having a content of Hethallylsulfonsäure and good pigment-dispersed filaments produced and der.Ausflockungsgrad of the pigment particles in the otherwise made filaments were examined MLT means of a Elektronenaikroskopes It was * bnla detected as Erge, that the particles were more finely dispersed in the strawberry, and it is believed that the difference in the degree of flocculation has an influence on the rub fastness of the fiber. Although the mechanism by which this difference arises is not clear, it is believed that a polymer with a strong protective effect in relation to the pigment particles associated with the ddjp 7er-

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division of the molecular weights of the polymer and the distribution of Forms constituents of the copolymer.

In the case of Haßspinnen using nitric acid as a solvent, it was found that the copolymer had a content of Hethallylsulfonic acid, in particular that using a Polymerization initiator of the system of hydroxylamine sulfonate and Lead sulfite made copolymer, only does a good job the rubbing fastness results, but also gives the dyed fibers a lively or shiny hue. It is assumed that this phenomenon is due to the good Diapergler-Markelt of the Plagmenttellohen.

Moreover, there was another surprising fact about it the hue of the fibers. This consists of the fact that, when a dyed fiber which has been 1-eally dried binder is attenuated, the hue becomes deeper. This tendency appears in a slightly different way old from the type of pigment used and is in the case of using Nitric acid as a solvent and a pigment of the phthalocyanine! «Ihe produced wet-spun, colored fibers considerable. The reason for this phenomenon has not been established, but it is believed that the phenomenon is related to the influence the change in the mutual effect of pigment parts and fiber structure or fiber structure is subject to or but the formation of micropores or hollow cavities closely associated with the wet-spun fibers produced using nitric acid as a solvent.

The term "pigment" used here refers to

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customary known inorganic or organic pigments and any inorganic components, such as cast iron and titanium dioxide, and organic pigments of the Honoazo series, Disazo series, Polyazo series, Phthalocyanine ihe, Anthraquinones ihe, Indigo series, dloacadiazine series, perylene series, ferynon series and Quinacridone series can be used. However, it is clear that a Pigaent, which changes color or pale in less time due to the action of the solvent, should not be used.

Bas pigment can be in the form of powder, paste or pulp, a solid dispersion in a suitable polymer or a powder thereof or in any other known form werdem, however, generally leads to the use of «Ines Pigmentes in powder form to reduce the spinnability of the solution and the use of a pigment in paste or pulp form preferred.

It is preferred that the particles of the pigment be smaller than 10 "in diameter, and it is particularly preferred that the pitch of the particles be smaller than 1" i. When the diameter exceeds 30M, the spinnability of the solution becomes great humiliated.

As mentioned above, the copolymer produced with a content of methallylsulfonic acid erfindungsgemlß particularly good ER ~ 2} -> * m * fi and in this case, the content of 0.1 to Methallylsulfonsjtnre betvagen to 2 wt £. If the Gehair is geria * ^ slz C, **, little effect is brought about and if the content is more than 2%, the stretchability of the threads at the time of spinning is reduced.

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low.

The acrylonitrile polymer can be made by any of the known ones Polymerization processes such as bulk polymerization, precipitation polymerization, Suspension polymerization, emulsion polymerization and solution polymerization using a solvent for the polymer.

The Polymerisationeinitiator which is suitable for use varies depending on the circumstances and known ä polymerization initiators such Perschwefölsäure, the ammonium or alkali metal salt of persulfuric acid, hydrogen peroxide, benzoyl peroxide, azo-bending 2.2 * (isobutyronitrile) or a A system composed of a water-soluble peroxide and a reducing sulfoxylic compound, for example a system composed of persulfate and acidic sulfite, hydroxylamine monosulfonic acid and / or disulfonic acid (hereinafter referred to as hydroxylamine sulfonic acid) or a system composed of hydroxylamine sulfonic acid and acidic sulfite Hydroxyureasulfonic acid or a salt thereof and a reducing sulfoxy compound can be used. If appropriate, a mercaptan, amine or a surface-active agent can be used as a polymerization aid. The temperature to be used during the polymerization and the pH value to be used during the polymerization vary greatly with the type of polymerization process used and the polymerization initiator used, but in general the temperature is -10 to 100 ° C and the pH value is 1 up to 7 »

The polymerization is preferably at 5 ° ^ ia 70 ⁰ C and at

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a pH of 2 to 4 is carried out when the aqueous precipitation polymerization using a system consisting of hydroxylamine sulfonate and bisulfite or a system consisting of flydroxyurea sulfonate and bisulfite is used as the polymerization initiator. The produced polymer, after being isolated and dried, is dissolved in a solvent, thereby forming a polymer solution results in · If the solution polymerization using * £ if »8 Solvent is used for the polymer, a polymer solution is of course immediately generated.

Any known solvent for the polymer may be used inorganic solvents such as nitric acid, aqueous zinc solution and aqueous Bhodanidlösung, and organic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, ethylene carbonate, succinic acid nitrile or sucein nitrile, Y-butyrolactone and kitromethane can be used. .

Bas pigment sum coloring is made by adding the polymer to a Dispersion of the pigment in a solvent, by simultaneously ge addition of the pigment and the polymer to a solvent or by adding the pigment to the polymer solution with the polymer mixed »Furthermore, the pigment can optionally be added during the polymerization. Furthermore, the so-called Master batch process are used

When hate pinning is practiced using nitric acid as the solvent, it is preferred to use nitric acid with a concentration of 65 to 75% by weight with a carbon content

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Do not use more than 0.000% nitrous acid as a solvent. If the nitric acid concentration is outside the above-mentioned limits, the pigment tends to discolour or pale and the polymer also tends to degrade. This is due to the fact that the concentrations of H ⁺ and NO- in nitric acid increase rapidly as the Concentration of nitric acid decreased below 68%, especially below 65%, due to the fact that the concentration of nitrating HO.NO ₂ increases rapidly when the nitric acid concentration is higher than 75%, and also due to the fact that a relatively high concentration Temperature sub-dissolving of the polymer is required if the nitric acid concentration is less than 65%. Ee 1st desirable that the polymer at a temperature lower than 10 ⁰ G, in particular lower than 5 ⁰ C dissolved and the at LSsung express? ® *? such a temperature is kept on reinforced idi ^ UW @ in the saltpeter consentmtlon outside the above mentioned GÄnaea is 94er the temperature of the polymer solution exceeds 10 ° 0, veslleri; the resulting pigment-dyed fiber has liveliness because of the color shade β due to the discoloration or pale pigment, (the degradation of the polymer and other undesirable lifting reactions.

Since the pigment particles in a nitric acid solution tend to flocculate catfish, let it be preferred The pigment is compared to a highly viscous polymer solution. ^ s ** ää «nd the lingering of the pigment in a polymer solution if possible take a course

The desired content of the Fignent varies with its type * and the use of the esseugtea dyed fibers, but it allows in

Generally not more than 10% by weight, in particular> 0 _t 1 to 5% by weight,

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¹² "166937b

sucked on the fibers.

- The raffle colored with a pigment is won by a Spinneret or multi-hole nozzle in a liquid coagulated bath spun or pressed or extruded and coagulated to form threads · The coagulated threads are usually used to bring about the liberation of solvents accustomed to desolvation in general with water and washed Threads are stretched with a stretch ratio of 4 to 16 in the heat. Swollen gel threads thus obtained become then cleaned.

In the cleaning step, which is an important feature of the invention, the threads are washed old with a cleaning solution and sometimes subjected to mechanical treatment so that the pigment particles exposed on the surface of the threads, ready to fall off, are removed. The means for increasing the speed of the flow of the cleaning solution on the surface of the threads and sub-stringing the threads increase the cleaning effect. Therefore, it is preferred not to put much tension on the cable during the cleaning step.

It is preferred to use a non-ionic or non-ionic or non-ionic detergent. Anionic agents such Katriumlaurylsulfat, HatriuBdodecylbenzolßulfonat or dodecylbenzolsulfonsauree sodium and Natriumstearät, nlcht-1onogene surfactants, such as sorbitan, Polyäthylenglykolst earal: _t Polyoxyäthylenlauryläther, DecaoxyäthyJ en <- oc tyl phenol ether and PolyoxyäthylensorbitanBonostearat: _t and a mixture of?. or more of these are used as cleaning agents.

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reversible. Among the non-ionic surface-active agents are advantageously those with an HLB value of 11 to used.

The cleaning temperature is preferably 40 to 9O ⁰ C, preferably 50 to 70 ° C * the cleaning 1st all the more effective is the longer of the Reinigungezeitraum, shows the effect of calibration, however, even at a cleaning period of several Secunda "Sometimes, the application of ultrasonic waves useful to increase the cleaning effect in a relatively short time. After cleaning, the threads can optionally be washed with water and treated with a textile oil and then dried.

It was found that the hue of pigment-dyed fibers varies widely with the drying conditions or the drying state, in particular with the drying temperature. Namely, if the drying ^{temperature is lower than 10O 0} C, the color tone of the dried fibers lacks depth and it is a little pastel-like (pastel), and if the drying ^{temperature is higher than KX) 0} C, especially higher than 110 ° 0, lot, then the color is deep and lively or shiny "the color varies in the range of iron Trocknimgstemperatüren bio 140 ⁰ C very little. If the drying temperature exceeds 15Q ⁰ C, the hue is reddish in total and these Naigung is considerable in the case of black fiber. Therefore · lot because most preferably, the first drying after spinning at a Teuperatur ν m 100 to 15O ⁰ O, particularly at a temperature of - 10 to WHERE, durchaufuhren ^0! O.

Dia gettooknötnrii threads feüuneu ^ egatienonfalii) srnaut goralnigt

0038 49/1769 BAD ORIGINAL - w..

and treated with a textile oil, mechanically depending on the circumstances curled and then dried. Dried threads thus obtained are then steamed.

The dampening, which is another important feature of the invention is carried out at 105 to 150 ° C with saturated or superheated steam. This steaming becomes «the purpose of the fixed fixation of those located on the surface of the threads Pigment particles in the fiber structure or in the pater structure and thus for the purpose of increasing the rubbing fastness and de * Spread of a deep and lively or shiny Shade of the fiber carried out. Therefore, steaming is of a very different nature than heat treatment in the loose state to prevent the shrinkage and to improve the properties which it gives acrylic fiber in general so that the threads are not always loosened.

The cleaned threads subjected to steaming can then optionally be subjected to a heat treatment for the purpose of improvement subjected to the properties, mechanically crimped and in the form of cable or staple fiber after cutting of a certain length for spinning.

The invention was made specifically on the basis of fibers with like Beatand parts described, however, oils is also based on conjugated fibers with a content of 2 or more than 2 types of polymer components applicable.

The invention is not to be construed as limiting in light of the following Examples to be understood are explained in more detail.

166937b

Belep! El 1

The following substances were continuously supplied to the first container of reaction containers made of stainless or corrosion-resistant steel with a stirrer at the following speeds. ^J

deionized water? 000 g / hour

Acrylonitrile $ 1 * g / SfÜilt Acrylic acid methyl ester or ' _eQ Methyl acrylate λ

■ ethallylsulfonsaurea sodium or ₆ · sodium methallylsulfonate

Sodium hydroxylamiimonosulfonate

white sodium hydroxylamine- 8 g / hour

■ onosulfonate

Sodium bisulfite 30 g / otunae Sulfuric acid 2 g / hour

The slurry in the first booster was continuously overflowed or allowed to emerge and introduced into the wide container. The slurry in the second container was allowed to overflow or discharge and * vlv separation of the polymer by filtration was passed through an Oliver filter Polymer obtained in a yield of 93%. After drying, this polymer consists of 7.8% by weight of methyl acrylate or methyl acrylate, 0.54% by weight of methallylsulph or acidic sodium or sodium sulphonate as well as acrylonitrile and a very small amount of salts as the remainder .

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2.4 kg of this polymer were added to 10 liters of 70% nitric acid (containing 0.0002% nitrous acid) at ⁰ ° C. and kneaded to dissolve it. The solution thus obtained was mixed with 360 g of commercially available black pigment paste containing 20 wt .- # sewer carbon black, defoamed by kneading for 3 hours and then filtered through a stainless or corrosion-resistant gauze with a mesh size of 0.041 mm (350 mesh), whereby a black spinning solution with a viscosity of 950 P was obtained O ⁰ C cooled · 32% nitric acid solution spun or pressed. The threads obtained were guided at a speed of 4 m / minute, washed with water and stretched at a stretching ratio of 12 in hot water at 90 °.

A part of the stretched FSden was dried as such and another part was dried after drying. The cleaning was carried out using an aqueous solution of 1 g / l Sc euro) 4OO _t which ifit a non-ionogeuea surfactant, by repeatedly dipping at 60 ⁰ C and that at a part of the threads during 10 minutes and at another part of the Threads for 10 seconds, as well as squeezing or pressing and subsequent washing with water

hie FSden WUI the beziehuugswfeiee using a cylinder dryer drying cylinder "In the heat at 130 ⁰ C to .the

Air dried. The dried threads were placed in a water bath

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of 60 ⁰ C with a content of a textile oil and then after dewatering or dehydration by means of squeegee rollers or dewatering presses in the heat at 110 ⁰ C in the air. Part of the dried filaments thus obtained was subjected to a heat treatment in a state of restricted shrinkage in an autoclave with saturated steam at 120 ° C. for 10 minutes. The rubbing fastness of the thread samples obtained in this way was measured. The results are compiled in Table 1 below. It follows from this table 1 that the. present invention is very useful.

Table 1

Attempt no. Cleaning
period Steaming Relbechtl
dry lead
wet 1 - £ 0 no Rating 3 Rating 2 • 1 - II O carried out Rating 3 Rating 2.5 1 - III 10 seconds no Rating 4 Rating 3 1 - IV 10 seconds carried out Rating 4.5 Rating 4 1 - V 10 minutes no Rating 5 Rating 3 1 - VI 10 mins carried out Rating 5 Rating 4.3

Example 2

Red swollen gel threads were spun and drawn in the same manner as in Example 1 except that a paste-like red pigment (Visoo scarlet 1401, manufactured by Dai-Nippon Minting Ink Mfg, Go », Ltd.) as the pigment was used. Dia filaments were 1 minute at ⁰ TO G goal using Jfatrlumdüdeojrlbansolaulfonafc basialningsweise tlodeti / i.ben / iOlnalfoTu.Hurom lfafc; b Viil.i '#;. * Lura g-. To you; minl ^ mu, {solution

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turned quite red 'and as a result of calorimetric analysis it was found that about 0.7% of the pigment was in the elongated Threads were exuded or excreted.

After washing with water, the threads were treated with a Textual, dried at 120 ° C. and then loosened a scratch treatment, subjected to 110 ° C with saturated steam The tro oken rubbing is called the eo obtained red thread had the Rating 5 and the fastness to scratching had the rating 4. The A- ' they took on a very rich red color.

The fastness to hate rubbing of a sample of the threads treated by steaming (without cleaning) had a rating of 2.5.

Example 3

The polymer produced in Example 1 (100 parts) was dissolved in a 5% aqueous solution of sodium rhodanide at 32 ° C. and the solution was kneaded, defoamed, filtered and with a black pigmentation containing channel soot then spun into a 10% sodium thiocyanate solution at ⁰ ° C. purified, dried, treated with an Textile * 1, steamed again and then dried at 125 ⁰ C. Also, a sample subjected only to cleaning and no steaming, a sample subjected only to steaming and no cleaning and a sample subjected to no cleaning and no steaming were prepared separately. The H »LI)) ohbh» U> of these samples is in the following TabuHe 2

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susasun posed. It can be seen from this Table 2 that the present invention is very effective.

Table 2

Try Mr. Clean Danpfen Reibechth
dry time
nat 5-1 carried out carried out Rating 4 Rating 4 5-11 carried out no Rating 4 Rating 3 3 - III no carried out Rating 3 Rating 2 5 - IV no no Rating 2 Rating 2

Example 4

7,000 g of deionized water with an addition of sulfuric acid, 636 g of acrylonitrile, 42 g of methyl methacrylate or methyl acrylate, were added to each of Bit's stirrer, reflux condenser and thermometer. 5t5 R Ratrluehydroxyharnatoffeulfonat beilehuncrBwelse hydroatyharnBiofisulionsaureε sodium, 42 _{tons of} sodium sulfite and the following amounts of "et-halljisulfonsäuren! Natrlua Ijeilehungewelee Hatriuem · thaiIyI-sulfonate were charged and the mixture was stirred at 53 ⁰ C for 5 hours, allowed to polymerize.

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A.) Sodium aethallylsulfonate or sodium methallylsulfonate

B.) methallylsulfoneaureβ sodium or sodium methallyl sulfonate

C.) Sodium methallylsulfonate or sodium methaiyl sulfonate

D.) sodium methallylaulfonic acid or sodium methallyleulfonate.

£ ·) Methallyl sulfoneaure s sodium or sodium methaiIyIeuifonat

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ο g

0.70 g 2.10 g 3.50 g

7.0 g

Each of the obtained slurries was dehydrated or dehydrated, washed with water and dried. So were 640 g of white powdery yellow polymer in the case of A.), 640 g the same in the case of B.), 630 g of the same in the case of C.)> 636 g of the same in the case of D.) and 618 g of the same in Case · from £ ·) received. The compositions of these polymers were as follows:

polymer Methacrylic acid methyl content
ester or methyl
methacrylate (in% by weight) Content of methallyleulfone
acidic sodium relation
Wise Sodium MethaiIyleul
fonat (in% by weight) A.) 6.5 0 B.) 6.4 0.06 C.) 5.7 0.24 D.) 6.6 0.35 E.) 6.7 0.65

Each of these polymers (130 g) was dissolved in 820 g 72% -> by weight aqueous nitric acid at 5 ⁰ C and the solution was 325 g pulverfSndgem bit Red "pigment (Cromophtal Bordeaux R, from Ciba Ltd."

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prepared), stirred, mixed, filtered through a filter made of stainless or corrosion-resistant steel with a mesh size of 0.041 mm (550 mesh) and defoamed, whereby a colored solution with a viscosity of Λ '200 P was obtained. This solution was through a Spinneret with 100 holes, each of which had a diameter of 0.1 mm, spun or pressed out at a spinning speed or extrusion speed of 5 »4 cm ^ / minute in 35% nitric acid cooled to -3 ° C. The coagulated filaments obtained were washed with water, guided at a speed of 5 m / minute, drawn with a stretching ratio of 8 in hot water at 100 ° C. for 10 seconds while passing them along; a train or thread feed (draft) of 1 _e O in Oji ^ -lgar aqueous solution of sodium stearate at 80 ⁰ C; and then dried at 130 ° C and the color tones of the samples were compared. While Samples D and E took on a red color which was not cloudy and not dark, respectively, and Sample C a little cloudy respectively

dark vote color, sample B was a little cloudy or dark and sample A was fairly cloudy or dark and assumed a less saturated red color. When the samples were then ^{steamed at 130 °} C., an increase in saturation was observed in all cases without changing the sequence. The dry rub fastness of samples A and B had the rating 2.5 «, that of sample C had the rating 3 and that of samples D and E had the rating 4.

The samples of threads A ¹ , B ', C ¹ , D ¹ and E · were prepared in the same manner, except that cleaning was omitted and the rockon-frictional fastness was not applied

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yon Α · and B * had the rating 2, that of O ¹ had the rating 2.5 and those of O * and S * had dl · rating 2.5 to 3 »

Example 5 Acrylonitrile 6 * 5.4 g Vinyl acetate 49.0 g

methallylsulfonsaurea sodium Borrowed sodium methallyl - 5.6 g sulfonate

A) The above-mentioned monomers were in the same manner as la Example 4 for 5 hours at 55 ° C and a pH value ▼ on 3.0 using the sodium hydroxyurea sulfonate / sodium bisulfite system3 or the System of sodium and hydroxyurea sulfonic acid Sodium bisulfite as a polymerization initiator and 7,000 g Water as a medium allowed to polymerize. Thus, 6? 50 g obtained white powdery polymer.

B) The white powdery polymer (660 g) was made in the same way as obtained under point A) above, except that 5.6 g of ammonium persulphate and 21.0 g of sodium are obtained as Polymerization initiator was used and the polymerization was carried out at 40 ° C. and a pH of 5.0 became.

C) The small powdery polymer (570 g) was passed through 7 stands polymerizing the above-mentioned monomers for a long time at 65 ° C. * <

and a pH of 2.5 using 2.10 g 2,2 * · <-Aio-bts-Cieobufcyronltril) as polyme »ieationeinitiawt> r _t /

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BATH ORIGINAL

3 »50 g lauryl reagent ale polymerization reg» and 2 100 g of water obtained as a medium "

Each of the polymers A), B) and C) was dissolved in 66% nitric acid at ⁰ ° C. in such a way that a solution with a glycol concentration of 16% by weight was obtained. yellow bensidine yellow pigment paste, sucked onto the polymer, set and kneaded. The colored Polyaerlojiung obtained was spun in the same manner as ia Example 4 and the threads wtftttn with a stretch ratio of 8 stretched at 7O ⁰ C using γοη polyoxy & thylensorbitanmonooleat ait 10 of polyoxyethylene tpolyozyethylene (10) purified aorbitan uonooleate] as a cleaning agent, ait water washed and then at 14O ⁰ C dried · the dried filaments were gedaspft at 130 ° C and the hue and Hifreeiitheit was compared.

Liveliness in a dazzling gleam of color! A) B) C)

The dry rub fastness τοη A) had the rating 5, that of B had a rating of 4 and that of C had a rating of 2.5.

Example 6

It was a copolymer consisting of 93 wt .- # acrylonitrile and 7 wt .-% vinyl acetate, using Katriuahydroxyharnetoffsulfonat as well as hydro ^ yurstoffsulfonsaurea HatriUB and acidic Hatriuasulf it as Poiyaerisationsinitiator prepared in the same way as ia Example 4 and 254 g of the The copolymers obtained were dissolved in 1,700 g of diethyl ether.

BAD ORIGINAL _p 009849/1769 - »- · _

The solution was mixed with 8 g of a pasty or doughy pigment (Hicrosol Bordeaux 3B, manufactured by Ciba Ltd.) and kneaded, defoamed, filtered and then in a 45% aqueous solution of clay Dime thy lac et amide, its temperature 10 ⁰ C was held, spun or pressed. The coagulated threads were washed sufficiently with water, guided at a speed of 5 m / minute and ^{stretched in hot water at 100 °} C. with a stretching ratio of 6. Some of the stretched filaments were dried as such and some of them were cleaned by repeated immersion in an aqueous solution of 1 g sodium stearate / liter at 65 ° C. for 5 minutes and squeezing or squeezing and washing Water dried. The filaments were immersed by means of a cylinder dryer or Trockenrylindere in the heat at 130 ° C in the air dried in a water bath having a content of a textile oil at 50 ⁰ C, crushed by means Abquetechwalzen or Entwässerungepressen and then on to heat at 110 ° C air dried

A portion of the resulting dried fibers was 10 Vi utes in an autoclave to steaming with saturated steam subjected at 120 ° C.

The Hess results of the Kaßreibechl in 1. the so obtained "n j'P" are compiled in the following table J *

H ■ · ή P / ". '"■» ■ M

BATH ORIGINAL

- 25 - Table 3

Attempt no. Clean Steaming Wet rub-proof fit 6-1 no no Rating 1.5 6 - II no carried out Rating 2.0 6 - III 5 minutes no Rating 2.5 6 - IV 5 minutes carried out Rating 3.0

Claim BATH ORIGINAL

009849/1789

Claims (1)

PATBHTAM3PJIÜCH 1. Process for the production of colored aoryl fibers " where a solution of an Acrylonitrllpolymer or «Ines Acryl» nitrile copolymer containing not less than 80% by weight of acrylonitrile, 0.1 to 2.0% by weight * methallyl sulfonic acid and 19.9 to Contains 0 8 wt .-? T of an ethylenically unsaturated compound, and a pigment in the polymer or mixed polymer, preferably in an amount of not more than 10% by weight, improves on this Polymer, is present, is spun, the threads are freed from solvent and the swollen QeIfäden are stretched in the heat, thereby gskennseichnet that ■ washes, dries and then with the swollen gel threads a temperature of 105 to 150 ° C steams.